The Influence of the effect of solute on the thermodynamic driving force on grain refinement of Al alloys

Grain refinement is known to be strongly affected by the solute in cast alloys. Addition of some solute can reduce grain size considerably while others have a limited effect. This is usually attributed to the constitutional supercooling which is quantified by the growth restriction factor, Q. However, one factor that has not been considered is whether different solutes have differing effects on the thermodynamic driving force for solidification. This paper reveals that addition of solute reduces the driving force for solidification for a given undercooling, and that for a particular Q value, it is reduced more substantially when adding eutectic-forming solutes than peritectic-forming elements. Therefore, compared with the eutectic-forming solutes, addition of peritectic-forming solutes into Al alloys not only possesses a higher initial nucleation rate resulted from the larger thermodynamic driving force for solidification, but also promotes nucleation within the constitutionally supercooled zone during growth. As subsequent nucleation can occur at smaller constitutional supercoolings for peritectic-forming elements, a smaller grain size is thus produced. The very small constitutional supercooling required to trigger subsequent nucleation in alloys containing Ti is considered as a major contributor to its extraordinary grain refining efficiency in cast Al alloys even without the deliberate addition of inoculants.The Australian Research Council (ARC DP10955737)

An epitaxial model for heterogeneous nucleation on potent substrates

© The Minerals, Metals & Materials Society and ASM International 2012In this article, we present an epitaxial model for heterogeneous nucleation on potent substrates. It is proposed that heterogeneous nucleation of the solid phase (S) on a potent substrate (N) occurs by epitaxial growth of a pseudomorphic solid (PS) layer on the substrate surface under a critical undercooling (ΔT ). The PS layer with a coherent PS/N interface mimics the atomic arrangement of the substrate, giving rise to a linear increase of misfit strain energy with layer thickness. At a critical thickness (h ), elastic strain energy reaches a critical level, at which point, misfit dislocations are created to release the elastic strain energy in the PS layer. This converts the strained PS layer to a strainless solid (S), and changes the initial coherent PS/N interface into a semicoherent S/N interface. Beyond this critical thickness, further growth will be strainless, and solidification enters the growth stage. It is shown analytically that the lattice misfit (f) between the solid and the substrate has a strong influence on both h and ΔT ; h decreases; and ΔT increases with increasing lattice misfit. This epitaxial nucleation model will be used to explain qualitatively the generally accepted experimental findings on grain refinement in the literature and to analyze the general approaches to effective grain refinement.EPSRC Centre for Innovative Manufacturing in Liquid Metal Engineerin

Microstructure and Phase Formation in a Rapidly Solidified Laser-Deposited Ni-Cr-B-Si-C Hardfacing Alloy

In this study, microstructural evolutions and phase selection phenomena during laser deposition of a hardfacing Ni-Cr-B-Si-C alloy at different processing conditions are experimentally investigated. The results show that even minor variations in the thermal conditions during solidification can modify the type and morphology of the phases. Higher undercoolings obtained at faster cooling rates suppressed the primary borides and encouraged floret-shape mixtures of Ni and Cr5B3 via a metastable reaction. Variations in the boride phases are discussed in terms of nucleation-and growth-controlled phase selection mechanisms. These selection processes also influenced the nature and proportion of the Ni-B-Si eutectics by changing the amount of the boron available for the final eutectic reactions. The results of this work emphasize the importance of controlling the cooling rate during deposition of these industrially important alloys using laser beam or other rapid solidification techniques. (C) The Minerals, Metals & Materials Society and ASM International 201

Active Mg Estimation Using Thermal Analysis: A Rapid Method to Control Nodularity in Ductile Cast Iron Production

Appropriate nodularity in ductile iron castings is strongly associated with the presence of high enough not combined Mg dissolved in the melt to cast. However, the residual Mg which is commonly measured for production control accounts for both dissolved Mg and Mg combined as oxides and sulfides. To account for the uncertainties associated with such a control, it is quite usual to over treat the melt with the risk of porosity appearance. A new methodology based on thermal analysis has been developed in the present work so as to estimate the amount of free Mg dissolved in the melt ready for pouring. A combination of Te mixture and a new “reactive mixture” composed of sulfur plus a commercial inoculant has been prepared for this purpose. This reactive mixture is able to transform the magnesium remaining dissolved in the melt to combined forms of this element. Experiments performed both during start of production (when Mg overtreatment is usual) and during normal mass production indicate that important variations of free Mg occur without relevant changes in residual Mg content as determined by spectrometry. The method developed in the present work has shown to be highly effective to detect those melt batches where active Mg content is not high enough for guaranteeing a correct nodularity of castings. Selection of proper active Mg thresholds and a correct inoculation process are critical to avoid “false”-negative results when using this new method

Grain refinement of magnesium alloys: a review of recent research, theoretical developments and their application

This paper builds on the ‘‘Grain Refinement of Mg Alloys’’ published in 2005 and reviews the grain refinement research onMg alloys that has been undertaken since then with an emphasis on the theoretical and analytical methods that have been developed. Consideration of recent research results and current theoretical knowledge has highlighted two important factors that affect an alloy’s as-cast grain size. The first factor applies to commercial Mg-Al alloys where it is concluded that impurity and minor elements such as Fe and Mn have a substantially negative impact on grain size because, in combination with Al, intermetallic phases can be formed that tend to poison the more potent native or deliberately added nucleant particles present in the melt. This factor appears to explain the contradictory experimental outcomes reported in the literature and suggests that the search for a more potent and reliable grain refining technology may need to take a different approach. The second factor applies to all alloys and is related to the role of constitutional supercooling which, on the one hand, promotes grain nucleation and, on the other hand, forms a nucleation-free zone preventing further nucleation within this zone, consequently limiting the grain refinement achievable, particularly in low solute-containing alloys. Strategies to reduce the negative impact of these two factors are discussed. Further, the Interdependence model has been shown to apply to a broad range of casting methods from slow cooling gravity die casting to fast cooling high pressure die casting and dynamic methods such as ultrasonic treatment

Grain refinement of deoxidized copper

This study reports the current status of grain refinement of copper accompanied in particular by a critical appraisal of grain refinement of phosphorus-deoxidized, high residual P (DHP) copper microalloyed with 150 ppm Ag. Some deviations exist in terms of the growth restriction factor (Q) framework, on the basis of empirical evidence reported in the literature for grain size measurements of copper with individual additions of 0.05, 0.1, and 0.5 wt pct of Mo, In, Sn, Bi, Sb, Pb, and Se, cast under a protective atmosphere of pure Ar and water quenching. The columnar-to-equiaxed transition (CET) has been observed in copper, with an individual addition of 0.4B and with combined additions of 0.4Zr-0.04P and 0.4Zr-0.04P-0.015Ag and, in a previous study, with combined additions of 0.1Ag-0.069P (in wt pct). CETs in these B- and Zr-treated casts have been ascribed to changes in the morphology and chemistry of particles, concurrently in association with free solute type and availability. No further grain-refining action was observed due to microalloying additions of B, Mg, Ca, Zr, Ti, Mn, In, Fe, and Zn (~0.1 wt pct) with respect to DHP-Cu microalloyed with Ag, and therefore are no longer relevant for the casting conditions studied. The critical microalloying element for grain size control in deoxidized copper and in particular DHP-Cu is Ag

Partitioning of titanium during solidification of aluminium alloys

The purpose of the present work is to compare the segregation behaviour of Ti solute in low solute alloys, such as nominally pure Al, and high solute alloys typical of Al-Si casting alloys. Microprobe measurements of Ti segregation within grains show that, under the solidification conditions employed, the measured partition coefficient of Ti in pure Al is 6·7 compared with the phase diagram prediction of ∼7·5. Similar measurements in an Al-7Si-0.3Mg alloy resulted in a partition coefficient of 3·2. Based on the measured partition coefficients, this translates into a reduction in the growth restriction factor (a measure of the segregating power of solute elements) from 8·75 K in pure Al to 3·36 K in Al-TSi-0·3Mg with an addition of 0·05 wt-%Ti. This may explain why Ti in solution is a less effective grain refiner in casting alloys than in low solute content wrought alloys. In addition, the measured Ti segregation profiles were compared with predicted profiles based on the Scheil or similar solidification relationships. It was found that the predictions of the Scheil equation produced a good fit with the measured Ti segregation profiles once it was adapted for the geometrical nature of dendritic solidification

Titanium sponge as a source of native nuclei in titanium alloys

Equiaxed β-grain morphologies have been observed in a wide array of Ti alloys produced by numerous solidification-based processes and, in terms of conventional solidification theory, are believed to be a consequence of heterogeneous nucleation upon native nucleant particles during solidification. In contrast, the source of these heterogeneous nuclei has yet to be established or explored in detail. In this work, titanium sponge was investigated as a possible common-denominator source of these nuclei. It was found that the native nuclei populations in titanium alloys may consist of transient interstitial-based compounds and fragments of titanium. A residual contaminant identified on the commercial titanium sponge pieces (sodium chloride), was also found to be effective at promoting smaller as-cast prior-β grain sizes